Methods of making a lignocellulose product and products resulting therefrom



ilnited States Patent METHODS OF MAKING A LIGNOCELLULOSE PRODUCT AND PRODUCTS RESULTING THEREFROM No Drawing. Filed Sept. 25, 1958, Ser. No. 763,192 2 Claims. (Cl. 106-163) This invention relates to methods of making a lignocellulose product and to the products resulting therefrom.

This application is a continuation-in-part of my copending application, Serial No. 443,711, filed July 15, 1954, now US. Patent No. 2,864,715.

It is an object of this invention to provide an improved method of making a moldable composition comprising reacting in the presence of steam an essentially dry mixture including comminuted lignocellulose and a reactant consisting essentially of ammonium hydroxide to split at least a portion of the lignin from the lignocellulose while confining the mixture of lignocellulose and reactant under superatmospheric pressure, preferably at about 300-550" F. for about 4-60 minutes.

Another object of the invention is to provide an improved method of making a molded composition comprising reacting in the presence of steam an essentially dry mixture including comminuted lignocellulose and a reactant consisting essentially of ammonium hydroxide to split at least a portion of the lignin from the lignocellulose while confining the mixture under superatmospheric pressure, finely dividing the resulting product and molding at an elevated temperature and pressure.

A further object of the invention is to provide lignocellulose products prepared by the above methods.

Other objects and advantages of the invention will be apparent from the following description of several embodiments of the invention.

An important advantage of the invention appears to be the controlling of the reaction so that the alpha cellulose is reduced in molecular size sufiiciently to prevent swelling of subsequently fabricated products but not to the extent that toughness of fibre is lost. This latter occurs under drastic degradation and starts to become quite serious when approximately 25% of the lignocellulose has been lost as either gaseous or soluble .byproducts. Another advantage appears to be the controlling of the cellulose degradation to plasticize the lignin component so that it can subsequently be made to flow and function as a binder between the comminuted lignocellulose particles.

Another advantage is the provision of a relatively dry system so that high capacity for the processing of, for example, wood waste is attained. This is not possible in a wet process such as ordinarily found in a pulping process in which the reactor is charged with approximately 90% water which takes up space as well as requires the addition of large amounts of energy to bring the reaction medium to the proper temperature.

Another advantage is the contacting of lignocellulose or dry mixes of lignocellulose and other ingredients under superatmospheric pressure with a vapor or combination of Vapors functioning both as a heat transfer medium and as a reactant.

A further advantage is the production of an extrudable composition wherein the reaction products may be extruded under a pressure of 2,00020,000 lbs. per square inch and in a temperature range of 400 duce shaped articles.

In the method of this invention an essentially dry mixture including comminuted lignocellulose and a reactant capable of breaking down at least a portion of the lignocellulose to provide lignin or modified lignin is reacted as by heating while confining the lignocellulose and the reactant under superatmospheric pressure as in an autoclave. During the reaction the lignocellulose bond is apparently broken and the lignin is released to operate as a binder.

It appears that the hemi-celluloses are the primary constituents of the lignocellulose which are attacked by hydrolysis, but that under the high pressure and temperature of this invention a portion of the hydrolysates are further converted to higher molecular Weight materials which can function as plasticizers for the autoclave product when it is molded. At the same time a controlled degradation of the alpha cellulose is carried out to the extent that the desired degree of moisture stability is obtained in the molded or extruded products without an unnecessary loss of toughness. These actions are believed to occur although they have not been absolutely proven.

The methods of this invention may be carried out batchwise in an autoclave or a sealed press or continuously in a continuous contactor.

The lignocellulose which appears dry to the touch actually contains up to about 30% water before the reaction begins.

The lignocellulose which may be used in. this invention includes wood as well as other lignocellulosic vegetable materials. The lignocellulose is finely divided so that the particles are preferably not more than 20 mesh in size as measured by a standard screen although smaller sizes are preferred.

During the reaction which takes place in a confined atmosphere under superatmospheric pressure various reaction products are produced although the exact nature of the reactions is not understood. It appears that the reaction products are either inert so that the product itself is inert, have a binding action such as is true of the lignin produced, are gaseous by-products, or are polymerized. By hydrolyzing and partially removing, or polymerizing the hemicelluloses to lignin type materials, the ratio of lignin and other binders to the alpha-cellulose is increased so that the general nature of the lignocellulose mixture is drastically changed.

The high pressure method of this invention has a number of advantages that are not possible with reactions taking place at ordinary pressures and in an unconfined state. In the preferred process, steam is introduced into the autoclave both for heating purposes and to supply moisture for the reaction. In the high pressure method of this invention heat transfer is much more rapid so that in general a shorter reaction time is required. Furthermore, energy losses during the reaction are greatly reduced. In the ordinary reacting mixture these energy losses result from the release of volatile materials such as water vapor, gaseous reaction by-products and the like. As the reaction here takes place in a confined atmosphere, no such losses occur to any material degree. Furthermore, the energy supplied by the steam or vapor is utilized to heat only the lignocellulose with its approximately normal moisture content in contrast to pulping type reactions where large quantities of water are present, requiring far greater expenditures of energy.

Another important advantage of this process is the close control that is obtained over the reaction. Thus the temperature of the reacting mass, and hence the rate of reaction, can be easily raised or lowered by controlling the rate of flow, pressure and the temperature of the heat F. to protransfer medium which may be steam, oil vapor, or other high temperature fiuids. Reactions may easily be stopped by flashing the heat transfer medium from the autoclave since the large energy loss on expansion cools the reacting mass below the incipient reaction point. During the practice of the process the reacting mixture may be confined in a jacketed vessel with the heating medium introduced to the chambers in the quantity and temperature desired.

'A very important advantage of the invention is that volatile reactants may be used as the reacting mass is in a confined space. Volatile reactants. are impossible, of course, when the reacting mass is in the open. As a result of the rapid heat transfer achieved by this invention and the penetration of volatile reactants the reaction not only. proceeds to completion in a much shorter time but the final product tends to be more uniform than where the reactants are heated such as in an ordinary process that depends upon surface temperature differentials.

Tests have shown that the confining of the reacting mass in the confined autoclave not only causes retention of the by-products of reaction within the mass even when the by-products are gaseous but also causes polymerization of all or a portion of these by-products, even some that are gaseous. In so-called wet processes large quantities of the by-products of reaction go into solution and are lost.

Another advantage of the'inventio-n is that the volatile by-products are easily collected and removed at low cost for later use where desired or to prevent the creation of a nuisance.

Where additional reactants and catalysts for the reaction are volatile no mechanical mixing of the ingredients is required. This results in a considerable saving in time, labor and other factors. Thus, in these instances, it is only necessary to charge the reactor with the lignocellulose and introduce the volatile materials including the ammonium hydroxide into the reactor under superatmospheric pressure. In addition, if desired, the reactants can be changed or modified during the course of a run. This is not possible to such a degree in a wet process where the charge generally contains less than 50% of lignocellulose, and addition of reactants would in many cases cause prohibitive amounts to gointo solution.

A further advantage of utilizing a vapor process is that the volatile content of the reaction product which is primarily moisture can be controlled. By using superheated steam with a sufficient degree of superheat, products on the order of 1% or lower volatile content can be obtained. Under normal conditions, 10 to 15 degrees of superheat at 300 pounds per square inch steam pressure will produce a product of 35% volatile content. Thus the expensive drying step connected with wet processes can be avoided.

Because of rapid penetration of reactants under high pressure, larger sized particles can becharged'to the autoclave than would ordinarily be used, and a savings in size reduction cost made as a result of lower power requirements to reduce the treated material in comparison with raw lignocellulose.

In addition, where flat stock or preformed material is being made as in a sealed press, the products can be made much thicker and more uniform than in an ordinary press which depends upon high platen temperatures for heat transfer, and in many cases requires almost prohibitive cycle times.

The ammonium hydroxide is preferably present as a 26 B. solution in water containing from 27-30% ammonia, but anhydrous ammonia in the gas phase could be introduced into the autoclave. The ammonium hydroxide is preferably used in an amount between 1.0- '-20.0% by weight of the lignocellulose.

I The products of the reactions of this invention may be finished shaped materials or moldable compositions that may be used to make molded products. Where the prodnet is molded after the reaction, this product is preferably removed from the reaction vessel and then ground to a fine powder that is preferably not over 50 mesh in size. The finely divided moldable material is heated to a temperature just sufficient to cause the material to fiow and fill the mold under the pressure used. This temperature is kept sufiiciently low, however, that losses are minor and breakdown due to decomposition is kept to a minimum. The preferred temperature is between 250-400* F. v I

The molding pressure may 'be any pressure suflicient to cause the material to fill completely the mold and will vary depending upon the shapeof the mold, the nature of the moldable material and other factors. In the preferred process to produce high density materials this .pressure is between 2,000-10,000 pounds per square inch. The molding time is only sufiicient to cause the moldable material to fill the mold and set, and again will vary depending upon the type of mold being used, the tempera ture, the nature of the moldable material and similar factors. In general, the molding time will vary between 02-15 minutes.

The flow of the moldable material of this invention is improved and a shorter time is required if a plasticizer is added. Thus, by adding 10% aniline to the finely divided moldable composition of this process the plasticity is increased. Similarly, the plasticity is improved by adding 10% furfural.

Plasticizers in general which have been found to be effective with the moldable materials include water; aromatic compounds containing a hydroxyl group such as aniline,phenol and cresol; alcohols such as benzyl, diethyleneglycol, glycerol, and furfuryl; nitrogen compounds such as formamide, urea, pyridine, and triethanolamine; and furfural.

The preferred plasticizers are water, furfural, aniline and phenol and the quantity utilized may vary depending onthe flow desired. The preferred quantity is between about 220%.

In particular, the choice of plasticizer will depend upon the end use or method of fabrication of the material. The reaction products themselves are of a slow thermosetting nature. Thus, if a plasticizer such as water which is incapable of thermoset is used, the material is essentiallyof a thermoplastic nature. This is also true of the preferred plasticizers as a group; however, when desired, thermoset compositions can be made by using furfural, aniline or phenol in conjunction with a catalyst and, if desired, other materials capable of copolymerization.

Materials which will function as catalysts include the oxides, hydroxides and carbonates of the alkali and alkaline earth metals. The preferred catalysts are the oxides of Zinc and magnesium.

Among the materials which may be "used with the thermosetting plasticizers as copolymers are hexamethylene tetramine, dimethylolurea, paraformaldehyde and urea.

Depending upon the set time required, about 0.55.0% of the catalyst and about 05-10% of the copolymer are used.

If desired, thermoset products can be obtained without the use of catalysts or copolymers merely by heat treating'the fabricated products after they have been molded or extruded.

If desired, products of density ranging from 0.2-1.3 specific gravity may be produced in the high pressure reacting vessel itself without requiring a subsequent molding operation as described above with high pressure molding. Here the finely divided lignocellulose and the reactant including ammonium hydroxide are mixed and the mixture cold pressed into the desired shape or compacted in a sealed press. The compressedmixture is then heated in the press or other high pressure vessel for the required time at the required temperature and pressure. The material when removed from the reaction vessel will then be found to be quite hard and strong.

Steam may or may not be supplied to the reaction vessel depending upon the result desired. If steam is used, it is preferably supplied at 100-1000 pounds per square inch pressure and at a temperature of 400550 F. In the event that a sealed press is used, the normal moisture content of the wood as well as the reaction by-products may be used to build up to a predetermined pressure which can be maintained constant by venting the excess vapors produced. This pressure is preferably between 100-600 pounds per square inch. Such a procedure eliminates the blow-ups encountered in treating Wood in an ordinary hot press at high temperatures, as well as drastically reducing press time, and polymerizes a percentage of the gaseous and low molecular weight byproducts to resinous-like materials which function as binders for lignocellulose particles. If desired, a two step process may be used in which the first step includes the pressure treatment and the second step includes venting the vapors to atmospheric pressure followed by a 2- 10 minute heat treatment period before removing the material from the press or the autoclave.

Example 1 in a heated autoclave and steam was admitted until the pressure was 300 pounds per square inch and the temperature was 425 F. The mixture was held under these conditions for 10 minutes and the interior of the autoclave was then vented. The reacting mixture was reweight lost during the reaction for several controls and several runs containing ammonium hydroxide. In both Examples 2 and 3, the ammonium hydroxide was mixed with the lignocellulose and autoclaved as specified in From the above table it is apparent that the presence of the alkali drastically reduces losses during the reaction. The ammonium hydroxide probably functions to buffer the lignocellulose-steam reaction, and thus prevent excessive degradation of the lignocellulose, although this has not been absolutely proven.

Where lignocellulose is reacted with ammonium hydroxide and sulfur and the reaction product is subsequently used to make a board in a hot press, the board possesses greater strength than where sulfur alone is used. The following table sets forth the composition and modulus of rupture of Example 4 in which 5% of ammonium hydroxide was used, and control C where only sulfur was reacted. The 20-mesh lignocellulose was blended with finely divided sulfur for A; hour in a ball mill prior to the addition of the ammonium hydroxide, and then [the blend was autoclaved as specified in Example 1.

Autoclave Press Percent Percent M.R., Example S NH OH p.s.i.

Time, Temp., Press, Time, Temp., Press,

Min. F. p.s.i. Min. F. p.s.i.

Control "0''... 10 0 20 440 300 10 400 157 4 10 5 20 440 300 10 400 40 458 moved from the autoclave and all particles which had Where sulfur is used with the lignocellulose-ammoconsolidated were thoroughly broken up. The material was then transferred to a disc-shaped mold and molded into a disc by heating at 450 F. and a pressure of 5,550 pounds per square inch for ten minutes. The resulting molded product was firm and hard and showed considerable resistance to Water and a high tensile strength.

The ammonium hydroxide is preferably used as a 26 B. solution. Based on the weight of the lignocellulose between 120% by weight of ammonium hydroxide may be added, with an especially preferred amount being 25-10% by weight of the lignocellulose. Where a smalleramount of ammonia is contained in the solution, the amount of solution used may be correspondingly higher. Similarly, when a greater amount of ammonia is present in the ammonium hydroxide solution, a corresponding lesser amount of solution may be used. If desired, the ammonia may be introduced as ammonia gas instead of as ammonium hydroxide solution. Where ammonia is introduced as a gas, a sufficient quantity should be used to give an amount of ammonium hydroxide with the moisture present so that the amount of resulting ammonium hydroxide is within the range specified. Whether ammonium hydroxide is used or ammonia is used as a gas, the same results are achieved as the gaseous ammonia unites with the moisture present to form ammonium hydroxide.

Where ammonium hydroxide is reacted with lignocellulose in the presence of steam, the weight lost by the lignocellulose during the reaction is reduced. The following table sets forth the autoclave conditions and the nium hydroxide reaction it is preferably added in an amount between 2-20% based on the weight of the lignocellulose.

In addition to sulfur, lignocellulose has been reacted 0 with ammonium hydroxide in conjunction with Vinsol,

lignin, cresol, or formaldehyde. In addition anhydrous ammonia gas has been used in place of the ammonium hydroxide solution. Examples 5, 6, 7, 8, and 9 in the following table illustrate the composition, and autoclave conditions under which these reactions were run.

Autoclave Percent Example NH OH Additive Time. Temp., Press., Min. F. p.s.i.

5% Vinsol 30 440 300 15% Lignin 25 448 300 5% Cresol 30 440 300 20% Formal- 20 440 300 dehyde. 9 40 p.s.i. None 30 440 300 Anhydrous Ammonia.

In the examples above the amount of additive used was based on the weight of the lignocellulose.

Where Vinsol and lignin are used they are preferably finely divided and are added in an amount equal to between 2-30% of the weight of the lignocellulose. Where cresol and formaldehyde are utilized the preferred amount is between l-25% of the weight of the lignocellulose.

In all of the above examples the-additive was blended with the lignocellulose for /2 hour in a ball mill before the addition of the ammonium hydroxide, and then further ball-milled for /2 hour to distribute the ammonium hydroxide throughout the mass. The blends were autoclaved as specified in Example 1.

In the methods of this invention the high pressure reaction may be used to treat the lignocellulose prior to molding but may also be used to chemically treat the lignocellulose without molding as the treated material itself has other uses such as employment as fillers in various plastic compositions. The method may also be used to produce products of a wide range of densities wherein the high pressure reaction and shaping is carried on at the same time.

Where the reaction takes place in an atmosphere of steam the volatile content of the resulting product may be reduced by using superheated steam. There is, of course, very little condensation with superheated steam.

The following table shows the reduction obtained in the volatile content of the product by operating with superheated steam:

All of the above runs were made with plain lignocellulose, but are typical of the results in general.

It was also found that when the reaction pressure is increased, the reaction time was considerably decreased. Thus, where ground lignocellulose was used with steam at 300 pounds per square inch and about 425-450 F. temperature as a reactant the reaction time was found to be minutes at this 300 pounds per square inch pressure. When the pressure was increased to 400 pounds per square inch, the reaction time was only about 7 minutes. Where the steam pressure was increased to 500 pounds per square inch, the reaction time was reduced to between 4-5 minutes. These steam pressures'were all gauge pressures.

The reaction temperaturesand times are controlled as desired to produce flow or moldability in the autoclave product and strength and stability in the final product. Thus, where the product is to be used as a molding material, it was discovered that under the above conditions with plain lignocellulose a reaction time of less than 20 minutes resulted in poor flow. But at this same steam pressure and using the same lignocellulose a reaction time of over 30 minutes produced a high quality moldable product. Apparently steam breaks down the lignocellulose so that the lignin acts as a binder while some of the hydrolized products of the reaction operate as plasticizers. In the high pressure confined atmosphere method of this invention, these reaction products are primarily retained. In the prior processes where a hydrolizing reaction was carried out either in the atmosphere or in a slurry, many of the by-products either passed off as gases or were dissolved and removed in the liquid. Thus by avoiding excess water the process of this invention results in the saving of substantial portions of the hemi-celluloses and make them available for use as plasticizers. However, if the reaction is carried on too long a time at too high a temperature, the hemicelluloses and other hydrolized products of the reaction tend to polymerize so that the final product exhibits lack of flow and is difficult to mold. The nature of these polymerizates is not completely understood.

Thus one of the advantages of the process of this invention is that it reduces losses of the lignocellulose and, furthermore, permits the use of lower molding pressures and temperatures when the reaction product is used as a molding composition.

Having described my invention as related to the embodiments set out herein, it is my intention that the invention be not limited by any of the details of description unless otherwise specified, but rather be construed broadly within its spirit and scope as set out in the accompanying claims.

I claim:

1. The method of making a moldable and extrudable composition, consisting essentially of: intimately mixing finely-divided essentially dry lignocellulose with a member of the class consisting of anhydrous ammonia and ammonium hydroxide equivalent to l.0-20.0% by weight of the lignocellulose of 26 B. ammonium hydroxide; and heating the resulting composition in the presence of steam at a temperature of about 300-550 F. in a confined atmosphere at a gauge pressure of between about -1000 pounds per square inch for between about 4-60 minutes to combine chemically a major portion of the ammonium hydroxide and the lignocellulose.

2. A moldable and extrudable product prepared by the method of claim 1.

References Cited in the file of this patent UNITED STATES PATENTS 2,708,637 Glab May 17, 1955 FOREIGN PATENTS 497,477 Great Britain Dec. 16, 1938 

1. THE METHOD OF MAKING A MOLDABLE AND EXTRUDABLE COMPOSITION, CONSISTING ESSENTIALLY OF: INTIMATELY MIXING FINELY-DIVIDED ESSENTIALLY DRY LIGNOCELLULOSE WITH A MEMBER OF THE CLASS CONSISTING OF ANHYDROUS AMMONIA AND AMMONIUM HYDROXIDE EQUIVALENT TO 1.0-20.0% BY WEIGHT OF THE LIGNOCELLULOSE OF 26* BE. AMMONIUM HYDROXIDE; AND HEATING THE RESULTING COMPOSITION IN THE PRESENCE OF STEAM AT A TEMPERATURE OF ABOUT 300-550*F. IN A CONFINED ATMOSPHERE AT A GAUGE PRESSURE OF BETWEEN ABOUT 100-1000 POUNDS PER SQUARE INCH FOR BETWEEN ABOUT 4-60 MINUTES TO COMBINE CHEMICALLY A MAJOR PORTION OF THE AMMONIUM HYDROXIDE AND THE LIGNOCELLULOSE. 